Calculated Defect Formation Energies Research Articles

Stepwise Optimization of Thermoelectric Performance in n‐Type SnS

AbstractTin sulfide (SnS) has been developed as an earth‐abundant and eco‐friendly compound that exhibits promising thermoelectric (TE) performance. While significant achievements are achieved in p‐type SnS, the development of its n‐type counterpart remains at a nascent stage, making it rather essential for developing n‐type SnS to ensure good compatibility in SnS‐based TE devices. In this study, Br is selected as the aliovalent dopant for realizing n‐type transport in SnS. Subsequently, isoelectronic Se alloying and vacancy compensation are utilized to further promote the TE performance for n‐type SnS. Se alloying can effectively narrow the bandgap of SnS for enhancing carrier concentration and diminishing thermal conductivity by strain and mass field fluctuations, while the excess Sn further compensates intrinsic Sn vacancies, thus optimizing carrier concentration and mobility simultaneously. These results are well verified by microstructure characterization and defect formation energy calculations. Consequently, the maximum ZT value of ≈0.7 and quality factor B of ≈1.02 at 823 K can be obtained after stepwise optimization, which is currently the highest value for n‐type SnS thermoelectrics. This study presents a significant progress for n‐type SnS and lays an important foundation for constructing all‐SnS‐based TE devices.

First-principles study of oxygen vacancy defects in β-quartz SiO2/Si interfaces

Abstract Understanding the electronic structures of gate oxides in Si-based devices is significant for improving device performance. We investigate the electronic properties of the oxygen vacancy defects in β-quartz SiO2/Si interface structure using first-principles calculations. The results indicate that the constructed (SiO2)4/(Si)4 structure is an indirect-gap semiconductor, with its band edges contributed by Si side and a large band-edge energy difference ( > 1.780 eV). Our study reveals that the presence of oxygen vacancy defects reduces the band gap, and V O 1 is transformed from indirect into direct band gap. The Si dangling bonds in V O 1 cause charge localization around the O vacancy, while the formation of Si–Si bonds in V O 2 and V O 3 lead to electron delocalization. In the calculation of defect formation energies, we find that V O 1 maintains the lowest formation energy across different states, making it more likely to form and structurally stable. Compared to O-rich environments, the formation energy in O-poor environments is overall reduced by approximately 4.5 eV, indicating that oxygen vacancy defects are more likely to form and be controlled under O-poor conditions. Our study emphasizes the importance of interface structure and defect characteristics in semiconductor research, providing insights for the development of Si-based devices.

Ab initio study on changing behaviors of lithium-rich layered composite cathode materials

The lithium-rich composite-layered oxide, xLi2MnO3•(1-x)LiM'O2, where M’ represents transition metals, is a promising cathode material with excellent capacity at high working voltage for lithium-ion batteries (LIBs). Nevertheless, an unusual charge-discharge feature is observed for this material with sloping and plateau regions during the initial charging. In this work, ab initio calculations based on density functional theory were employed to examine the stability of xLi2MnO3•(1-x)Li(Ni1/3Co1/3Mn1/3)O2 composite-layered cathode materials during the first charging. Optimized atomistic models for different compositions (x = 0.0, 0.3, 0.4, 0.5, 0.7, and 1) unveil a pseudo-rhombohedral or monoclinic-like structure within the solid solution phase, with simulated X-ray diffraction patterns closely matching experimental data. Using these atomistic models, the first charging process of the 0.4Li2MnO3•0.6Li(Ni1/3Co1/3Mn1/3)O2 cathode were investigated. There exists phase transition from a layered to a spinel structure. Additionally, Bader charge analysis reveals intriguing trends during the first delithiation process, where the valence states of Ni and Co gradual increase, while that of Mn almost remains unchanged. Simultaneously, significant oxidation of O is observed. This finding leads to further evaluations on oxygen vacancy formation in comparison to the energy required for delithiation. Defect formation energy calculations demonstrate that the plateau in charging curve is resulted from oxygen vacancy formation during the first charging. By empirical fitting oxygen chemical potential at μO = -1.200 eV, the calculated charging-discharging curves aligned well with experimental data during the first and second charging. Furthermore, the pathways of lithium and oxygen deintercalation are elucidated. This work contributes fundamental understandings on the xLi2MnO3•(1-x)LiM'O2 composite-layered oxides as cathode for LIBs, providing valuable guidance for further developments in high-capacity Co-lean cathode materials.

Microscopic damage in eutectic SnPb alloy: First-principles calculations and experiments

This study aims to comprehensively elucidate the microscopic origins of damage in eutectic SnPb alloy through atomic-scale investigations, a crucial endeavor for enhancing the alloy’s properties and furthering the development of Pb-free solders. First-principles calculations based on density functional theory (DFT) were employed to examine the mechanical constants and defect formation energies of the Pb phase, the β-Sn phase, and potential Sn/Pb eutectic phases in the SnPb alloy. The Voigt-Reuss-Hill approximation was utilized to derive the mechanical parameters of the elastically stable structure in SnPb alloy, facilitating the prediction of its mechanical properties. The defect formation energy calculations revealed a higher difficulty in forming vacancy defects in the β-Sn phase compared to the Pb phase. This discrepancy can be attributed to the stronger interactions between Sn atoms, resulting in the formation of more stable Sn-Sn bonds, thereby impeding vacancy generation in the β-Sn phase. Furthermore, the Pb phase exhibited a tendency for Sn atoms to occupy octahedral interstitial sites, whereas in the β-Sn phase, Pb atoms tended to displace neighboring Sn atoms along the [110] orientation into adjacent interstitial sites and occupy their lattice positions. Experimental observations complemented these calculation findings, demonstrating significant Sn element presence, up to 27.22 at%, in the Pb-rich phase, with notable microvoid damage primarily concentrated within this region. This observation aligns with the conclusions drawn from first-principles calculations and unveils the microscopic origins of damage in eutectic SnPb alloys.

Effects of oxygen vacancies on the structural, electronic, and optical properties of the photocatalytic InTaO4 compound

We conducted first-principles calculations based on density functional theory to investigate the impact of the oxygen vacancies on the structural, electronic, and optical properties of the InTaO4 compound. The latter is a famous photocatalytic semiconductor with its optical absorption in the visible range being an object of controversial interpretations. The presence of two types of isolated oxygen vacancies, O1 and O2, occupying 4g(1) and 4g(2) Wyckoff positions respectively, has been simulated within the frame of the supercell approach. Electronic structure and optical absorption (OA) have been calculated using the Becke-Johnson exchange-correlation potential. It is found that the presence of both types of vacancies generates defect states (DS) inside the band gap, primarily involving In-6s and O-2p states. The calculated valence-to-conduction-band band gap (4.25 eV) and DS-to-conduction-band band gap (2.5 eV) closely align with the experimentally determined OA edges for two onsets of InTaO4 absorption. The analysis of the calculated OA spectra leads to the conclusion that only O1 vacancy-induced absorption is consistent with the experimental OA, while O2 vacancy-induced absorption appears absent. This discrepancy probably arises from a higher concentration of O1 vacancies formed during crystal growth, attributed to the fact that the calculated defect formation energy of O1 vacancy is 0.258 eV lower compared to O2 vacancy. Consequently, the photocatalytic activity of InTaO4 is ascribed to intrinsic defects, primarily O1-type vacancies, though the influence of other defects cannot be entirely ruled out.

Exploring the effective P-type dopants in two-dimensional Ga2O3 by first-principles calculations

Exploring effective p-type doping in Ga2O3 is crucial for both fundamental science and emerging applications. Recently, N and Zn elements have been shown to exhibit considerable contributions to effective p-type doping in 3D Ga2O3 experimentally and theoretically, whereas the studies of their doping behaviors in 2D Ga2O3 are rare. In this study, we investigate the possibilities of N and Zn elements to achieve effective p-type doping, manifesting in the introduction of shallow acceptor levels typically less than 0.5 eV in 2D Ga2O3 using first-principles calculations with the generalized gradient approximation + U method. The calculated defect formation energies suggest that the N-doped 2D Ga2O3 structures are more easily formed under Ga-rich conditions, while the Zn-doped structures are more readily generated under O-rich conditions. Moreover, the introduced N and Zn atoms preferentially incorporate on the threefold coordinated OII and pyramidally coordinated GaI sites, accompanying with N3− and Zn2+ oxidation states in 2D Ga2O3, respectively. In particular, the electronic structures indicate that the occupied N-2p and semi-occupied Zn-3d orbitals produce shallow hole levels ranging from 0.09 to 0.33 eV, demonstrating that N and Zn atoms can behave as effective p-type dopants in 2D Ga2O3. The magnetic moments for N- and Zn-doped 2D Ga2O3 are 1.00 μB due to the doping of one hole, where the magnetic moments can be mainly attributed to the N atom and the nearest O atoms, respectively. Our work may offer theoretical guidance for the design of p-type 2D Ga2O3 materials and shed light on its potential optoelectronic and magnetic applications.

Oxygen Diffusion in Li(Nb,Ta)O3 Single Crystals

Oxygen tracer self‐diffusion in LiNbO3, LiTaO3, and LiNb0.15Ta0.85O3 single crystals between 880 and 1050 °C is investigated. 18O2 isotope‐exchanged samples are analyzed by secondary ion mass spectrometry. The diffusivities of each of the three different materials can be described by the Arrhenius law with an activation enthalpy of diffusion of about 3.2–3.5 eV. The diffusivities are highest for LiNbO3 and are lower by about one order of magnitude for LiNb0.15Ta0.85O3 and LiTaO3. The change of the pre‐exponential factor is identified as the reason for the difference in diffusivities. The experimental results are compared to defect formation energy calculations as given in literature and to energy barrier calculations for the diffusion of a single O vacancy as determined by nudged elastic band calculations based on density‐functional theory. An oxygen vacancy mechanism is suggested to govern diffusion. The difference in diffusivities is tentatively attributed to a different number of freely migrating vacancies, probably due to defect complex formation.

Development of magnetic La doped Al2O3 core-shell nanoparticle loaded hydrogel for selective recovery of fluoride from aquatic medium

The selective removal of pollutants from water bodies is regarded as a conciliation between the rapid expansion of industrial activities and need of clean water for sustainability. Fluoride is one such geogenic pollutant, and various materials have already been reported. Developing an efficient field employable material is however a challenge. Herein, we report the synthesis and competencies of strategically designed magnetic La-doped Al2O3 core-shell nanoparticle loaded polymeric nanohybrid as a benchmark fluoride sorbent. A facile synthesis strategy involved fabrication of Fe3O4 magnetic core followed by growth of La doped Al2O3 shell using sol-gel method. Doping of La2O3 into Al2O3 structure was optimised (6%), resulting in Fe3O4-Al0.94 La0.06O1.5 core-shell particles which provided exceptional fluoride affinity. The obtained magnetic Fe3O4-Al0.94La0.06O1.5 core-shell nanoparticles were then loaded (22%) into alginate to form cross-linked hydrogel beads (Fe3O4-Al0.94 La0.06 O1.5-Ca-ALG). These prepared hydrogel beads were characterised and utilized for selective recovery of fluoride under different ambient conditions. Driving forces for enhanced fluoride uptake by La doped Al2O3 were investigated and explained with the help of both experimental observation and theoretical simulation. Density functional theory calculations indicated significant expansion in the cell volume of Al2O3 due to La doping which favoured the fluoride sorption. The calculated defect formation energy for the incorporation of F into Al2O3 was found to decrease in the presence of La. XPS analysis suggested direct interaction of fluoride with Al, forming Al-F bond and breaking Al-O bond. Different vital parameters for uptake were optimised. Also, kinetics, isotherm and diffusion models were evaluated. Developed hydrogel beads attained record sorption capacity of 132.3mgg-1 for fluoride. Overall, excellent stability, no leaching of constituents, effectiveness for selective fluoride recovery from groundwater, brand it a perfect epitome of sustainable water treatment application.

Thermal transport of defective β-Ga2O3 and B(In)GaO3 alloys from atomistic simulations

β-Ga2O3 is a new generation of semiconductor material with a wide bandgap of 4.9 eV. However, the β-Ga2O3 devices inevitably produce defects within them after irradiation, leading to changes in their thermal conductivities. At present, the effect of radiation-damage-induced defects on thermal conductivity of β-Ga2O3 has not been carried out. Herein, we have employed molecular dynamics simulations to investigate the impact of defects on the thermal transport of β-Ga2O3, and the obtained thermal conductivity of non-defect β-Ga2O3 is in good agreement with recent reports. Our findings indicate that the thermal conductivity of β-Ga2O3 at room temperature exhibits a consistent decrease with an increase in the concentration of Ga vacancies, but shows a decreasing and then increasing trend as the number of O vacancies increases. In addition, doping/alloying is found to improve the irradiation resistance of β-Ga2O3 based on reported defect formation energy calculations, so the mechanism of alloying effect on the thermal conductivity is deeply analyzed through first-principles calculations. Moreover, the lattice thermal conductivities of ordered InGaO3 and BGaO3 alloys are predicted by solving the phonon Boltzmann transport equation. The obtained results that κ(Ga2O3) = κ(BGaO3) > κ(InGaO3) are attributed to the combined effect of volume, specific heat capacity, group velocity, and phonon lifetime of the three materials. This work can help to disclose the radiation damage influence on thermal properties of β-Ga2O3 semiconductors.

A review of first-principles calculation methods for defects in semiconductors

Doping and defect control in semiconductors are essential prerequisites for their practical applications. First-principles calculations of defects based on density functional theory offer crucial guidance for doping and defect control. In this paper, the developments in the theoretical methods of first-principles semiconductor defect calculations are introduced. Firstly, we introduce the method of calculating the defect formation energy and finite-size errors to the formation energy caused by the supercell method. Then, we present corresponding image charge correction schemes, which include the widely used post-hoc corrections (such as Makov-Payne, Lany-Zunger, Freysoldt-Neugebauer-van de Walle schemes), the recently developed self-consistent potential correction which performs the image charge correction in the self-consistent loop for solving Kohn-Sham equations, and the self-consistent charge correction scheme which does not require an input of macroscopic dielectric constants. Further, we extend our discussion to charged defect calculations in low-dimensional semiconductors, elucidate the issue of charged defect formation energy divergence with the increase of vacuum thickness within the jellium model and introduce our theoretical model which solves this energy divergence issue by placing the ionized electrons or holes in the realistic host band-edge states instead of the virtual jellium state. Furthermore, we provide a brief overview of defect calculation correction methods due to the DFT band gap error, including the scissors operator, LDA+<i>U</i> and hybrid functionals. Finally, in order to describe the calculation of defect formation energy under illumination, we present our self-consistent two-Fermi-reservoir model, which can well predict the defect concentration and carrier concentration in the Mg doped GaN system under illumination. This work summarizes the recent developments regarding first-principles calculations of defects in semiconducting materials and low-dimensional semiconductors, under whether equilibrium conditions or non-equilibrium conditions, thus promoting further developments of doping and defect control within semiconductors.

Physics of band-filling correction in defect calculations of solid-state materials.

In solid-state physics/chemistry, a precise understanding of defect formation and its impact on the electronic properties of wide-bandgap insulators is a cornerstone of modern semiconductor technology. However, complexities arise in the electronic structure theory of defect formation when the latter triggers partial occupation of the conduction/valence band, necessitating accurate post-process correction to the energy calculations. Herein, we dissect these complexities, focusing specifically on the post-process band-filling corrections, a crucial element that often demands thorough treatment in defect formation studies. We recognize the importance of these corrections in maintaining the accuracy of electronic properties predictions in wide-bandgap insulators and their role in reinforcing the importance of a reliable common reference state for defect formation energy calculations. We explored solutions such as aligning deep states and electrostatic potentials, both of which have been used in previous works, showing the effect of band alignment on defect formation energy. Our findings demonstrate that the impact of defect formation on electronic structure (even deep states) can be significantly dependent on the supercell size. We also show that within band-filling calculations, one needs to account for the possible change of electronic structure induced by defect formation, which requires sufficient convergence of electronic structure with supercell size. Thus, this work emphasizes the critical steps to accurately predict defect formation energy and paves the way for future research to overcome these challenges and advance the field with more efficient and reliable predictive models.

First-principles prediction of enhanced photocatalytic activity in La-X (X = Sc, V, Cr, Mn, Fe, Co, Ni, or Cu) Co-doped SrTiO3

The influence of La-X (X = Sc, V, Cr, Mn, Fe, Co, Ni, or Cu) co-doping on the electronic structure and photocatalytic activity of SrTiO3 system was investigated using the open-source software package Quantum Espresso (QE) based on density functional theory. Defect formation energy calculations showed an energy advantage for co-doped systems under Ti-poor and O-rich conditions. The La-V, La-Cr, La-Mn, La-Fe, and La-Ni co-doped systems showed magnetic properties with corresponding total magnetization of 0.08 µB, 2.97 µB, 3.30 µB, 1.00 µB and 1.00 µB, respectively. The La-X (X = V, Cr, Mn, Fe, Ni, or Cu) co-doped system exhibits photoabsorption activity in the visible region as compared to the pure SrTiO3. The La-X (X = Cr, Fe, Ni, or Cu) co-doped SrTiO3 exhibits a long carrier lifetime, especially the La-Fe co-doped system with a high effective mass ratio of holes to electrons of 5.79. However, the redox potential of the water decomposition reaction of the La-Cu co-doped system is too large, making it unsuitable for water splitting. In summary, the La-X (X = Cr, Fe, or Ni) co-doped systems exhibited intermediate states in the band structure and density of states, which better meet the specific requirements for photocatalysis compared to systems without intermediate states, showing superior photocatalytic potential. The band edge alignment of the three co-doped systems with water redox potentials demonstrated good matching. These findings suggest that La-X (X = Cr, Fe, or Ni) co-doped SrTiO3 is a promising candidate material for solar-driven water splitting.

Oxygen vacancy induced luminescence in Y2Zr2O7 and its removal on Eu3+ doping leading to enhanced quantum efficiency

To circumvent the low color rendering index and high color temperature of existing white light emitting diodes (LEDs), a lot of attention has been given on designing efficient red emitting luminophores for phosphor converted LEDs (pcLEDs). Utilizing the favorable properties of Y2Zr2O7 (YZO) pyrochlore and Eu3+ as dopant ion we could produce bluish white light emitting YZO and red light emitting YZO:Eu3+ (YZOE). Based on monoexponential luminescent decay, we could infer europium ion occupies Y3+ site which is in line with density functional theory (DFT) calculated defect formation energy and positron annihilation lifetime spectroscopy (PALS). YZO on UV irradiation generates bluish white light endowed by both neutral and singly ionized oxygen vacancies but with very meager photoluminescence quantum yield (PLQY∼1.2%). On doping Eu3+ ion in YZO; oxygen vacancy is completely removed with efficient host to dopant energy transfer leading to bright red emission with PLQY∼ 8.2%. The feasibility of YZO to Eu energy transfer is well established using DFT calculations. Reduction in density of oxygen vacancies on doping is well corroborated using electron paramagnetic resonance (EPR) and thermoluminescence (TL) spectroscopy and very well supported by DFT calculations. In this work by harnessing the potential of pyrochlore lattice defects and doping engineering we could enable almost 8-fold increase in PLQY in YZOE.

Defect formation energies of Ag- and Sr-doped 3C-SiC: A first-principles study

In this study, we conduct calculations of Ag- and Sr-doped in 3C-SiC using density-functional. To model defective systems, we dope Ag and Sr atoms in substitutional and interstitial sites. We use a supercell model consisting of 64 atoms and relax all atoms so that the atomic forces are less than [Formula: see text][Formula: see text]eV/Å. Then, we calculate the defect formation energies for each system. The calculated defect formation energies are 5.67[Formula: see text]eV and 7.77[Formula: see text]eV for substitutional Ag and Sr, respectively. In the case of the interstitial sites, the lowest defect formation energies are 10.36[Formula: see text]eV (Ag) and 14.63[Formula: see text]eV (Sr). We conclude that Ag and Sr are energetically favorable to be trapped at the substitutional site. Furthermore, the substitutional configuration of Ag is more stable than that of Sr. We check the converged value of the defect formation energies using a 216-site supercell and find that the energy difference is only 0.21[Formula: see text]eV. Thus, the 64-atom supercell is reliable for the calculations.

Sb-doped β-SrZrS3 as a low-toxic and low-priced absorber for intermediate band solar cells: A first-principles investigation

Intermediate band solar cell (IBSC) has received wide attention since it is considered as a feasible approach to overcome the Shockley-Quisser limit. Here, by using the first-principles calculations with HSE06-type hybrid functional, our calculated band gap of 2.04 eV is in line with the experimental result and demonstrates that β-SrZrS3 is a suitable host for the absorber of IBSC. A separated and partially-filled intermediate band(IB) is inserted into the forbidden gap of β-SrZrS3 after Sb replacing at Zr site (SbZr). Due to the presence of the IB, three-photon absorptions can be achieved in SbZr-doped SrZrS3 and the corresponding optical absorption coefficient matches the solar light spectrum adequately. Moreover, our calculated defect formation energy of SbZr is 0.94 eV, which is lower than that of SbS or SbSr under Sr-poor, Zr-poor and S-rich condition. Finally, Sb-doped β-SrZrS3 is recommended as a prospective low-toxic and low-priced absorber for IBSC.

Analysis of the electronic structure of β-SiO2 intrinsic defects based on Density Functional Theory

In order to characterize the effect of β-SiO2 intrinsic defects on the properties of the perfect structure, the electronic properties of the perfect β-SiO2 and its four typical intrinsic defects under the generalized gradient approximation (GGA) based on Density Functional Theory (DFT) were performed, and the defect formation energy, energy band, density of states (DOS) and differential charge density were calculated. The defect formation energy calculation results showed that interstitial defects were easier to form but less stable than vacancy defects. Meanwhile, the analysis of energy band and DOS indicated that the perfect and defective structures of β-SiO2 were indirect band gap insulators. Furthermore, the appearance of DOS at the Fermi level in the silicon interstitial structure and the energy band passing through the Fermi level indicated that the conductivity of the structure was improved. Moreover, the study of differential charge density illustrated charge transferred from silicon atoms to oxygen atoms, and Si-O covalent bonds with strong polarity were formed between silicon and oxygen atoms. Our studies could provide a theoretical basis for the study of the evolution of intrinsic defects and damages in ultra-precision machining such as ion beam figuring.

Probing site-selective doping and charge compensating defects in KMgF3: insights from a hybrid DFT study.

Design of optoelectronic materials with tunable properties using activators and defect clusters has become one of the prime interests of current research. In this study, detailed Density Functional Theory based calculations have been presented to investigate the geometries and electronic structures of various possible defect clusters using Eu-KMgF3 as a probe which has numerous technological and industrial applications. Using a more reliable hybrid density functional, we have calculated defect formation energies and thermodynamic transition levels to get knowledge about the site selectivity of Eu. It has been observed that the electronic structure of Eu-KMgF3 is not only dependent on the site of doping but also on the oxidation state of Eu (2+/3+). The present study also investigates the relative stability of different kinds of defects and defect clusters under various synthetic growth conditions. The ultimate aim is to find out the microscopic origin of the fundamental optical properties of Eu-KMgF3 and provide an unambiguous explanation of available experimental results. Thus, it has been revealed that doping with Eu results in the spontaneous formation of intrinsic defects, which contribute to the observed optical behaviour. We have also extended our study to investigate the role of codoping with Li in determining the geometry and electronic structure of Eu-KMgF3 aiming to explain its impact on the optical properties. Thus, a complete presentation of the influence of the activator in the absence and presence of lattice defects on the optical properties of KMgF3 has been accomplished in the current study. We strongly believe that the present study will be helpful in designing tunable phosphor materials by a defect-controlled synthesis strategy.

Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO2 and DFT calculations.

In recent times, ultra-thin films of hafnium oxide (HfO2) have shown ferroelectricity (FE) attributed to the orthorhombic (o) phase of HfO2 with space group Pca21. This polar o-phase could be stabilized in the doped thin film of the oxide. In the present work, both polar and non-polar o-phases of HfO2 could be stabilized in Gd-doped bulk polycrystalline HfO2. Rietveld analysis of XRD data shows that the relative population of o-phases in the presence of the monoclinic (m) phase of HfO2 increases with increasing Gd-content. The local environment around the host atom has been investigated by time differential perturbed angular correlation (TDPAC) spectroscopy, synchrotron based X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) measurements showed a reduction in grain size with increasing Gd-dopant indicating a solute drag effect. It could be established that the segregation of the Gd-dopant in the grain boundary is a thermodynamically favorable process and the solute drag effect plays an important role in nucleation of the o-phase in bulk HfO2. Stabilization of Gd in both Pbca and Pca21 phases of HfO2 was supported by defect formation energy calculations using density functional theory (DFT). The present study has important implications in future applications of HfO2 in ferroelectric devices and in understanding the role of dopants in stabilizing the o-phase of HfO2 in the bulk.

Insights into Cation-disorder effect on stability, electronic structure and defect properties of Zn-IV-nitrides: The case of ZnGeN2

Structural, electronic and intrinsic defect properties of ZnGeN 2 in different space groups are systematically studied using first-principles calculations. Accessibility of cation-disordered structure is verified by formation enthalpy calculations and the rather low formation energies of cation antisite defects. Furthermore, the electronic structures and intrinsic defect properties of ZnGeN 2 semiconductors in all the space groups can be well regulated by cation-disorder. The band gap of ZnGeN 2 can be significantly reduced by cation-disordering. Cation-disordering is revealed to weaken Zn 3 d -N 2 p antibonding at the valence band maximum and enhance the bonding at the conduction band minimum. Electronic structures, as well as associated physical properties, are intimately related to the chemical environment of N atoms. The nonstoichiometrically coordinated N atoms produced by cation disordering show significant influence on the stability and electronic structure of ZnGeN 2 . Our predictive results may inspire further experimental and theoretical exploration on the potential applications of ZnGeN 2 in optoelectronics. • Accessibility of cation-disordered ZnGeN 2 is confirmed by formation enthalpy and defect formation energy calculations. • Zn-IV-N 2 exhibit good modulation in their electronic structures and intrinsic defect properties by cation-disorder. • Cation-disordering is revealed to weaken Zn 3 d -N 2 p antibonding at the valence band maximum and enhance the bonding at the conduction band minimum. • The electronic structures as well as associated physical properties are intimately related to the chemical environment of N atoms.

Properties of Oxygen Vacancy and Hydrogen Interstitial Defects in Strontium Titanate: DFT + Ud,p Calculations

This work presents extensive theoretical studies focused on the mixed ion-electron transport in cubic strontium titanate (STO). A new approach to the description of this difficult system was developed within the framework of linear-scaling Kohn–Sham density functional theory, as realized in the ONETEP program. The description we present is free of any empirical parameters and relies on the Hubbard U and Hund’s J corrections applied to both Ti and O atoms. The proposed methodology was validated by considering perfect STO. Its calculated properties were found to be in close agreement with experiments and calculations at higher levels of theory. The validated approach was subsequently employed to study the oxygen vacancy (VO) and the hydrogen interstitial (IH), using very large supercells (625 ± 1 atoms). The relaxed configurations of defects were obtained through fastidious energy minimization and later analyzed from a number of perspectives. The calculated defect formation energies and charge transition levels (CTLs) were found to be in close agreement with the experiment. With the exception of the charge-neutral VO, all considered defects were found to introduce shallow states, located down to 0.2 eV below the conduction band. Our calculations revealed a large 1 eV difference in the thermodynamic and optical CTLs of the neutral VO, explaining the inconsistencies observed─till now─between conduction and spectroscopic measurements. The influence of defects on the bonding characteristics and the crystalline structure of STO was quantified, revealing that both VO and IH defects lead to a significant polarization and strong tilting of the TiO6 octahedra.